Metallized acid polyazo dyes



Patented Oct. 21, 1 941,

UNITED STAT PATE MET'ALLIZED ACID PQLYAZO D'YES- Moses L. Crossley,Plainfield, and Lincoln M.

, Shafer, Upper Montclair, N. J., assignors to.

American, Cyanamid Company, New York, N. Y., a corporation of ;Maine NoDrawing.

Application October 31, 1939, Serial No. 302,134 r 13 Claims. (01.260-145) This invention relates to metallized polyazo' The metallizeddyes of the present invention are obtained by metallizing a polyazodyehaving a middle component which is a dihydroxy aryl compound capable,of combining with two molecules of diazo compounds in positions orthoto the hydroxy groups, at least one of the diazo compounds having ametallizable group such as a hydroxyl or carboxyl group ortho to the azogroup and at least one end component containing' a'solubilizing group.The dyes may be represented by the following general structural iormula:p

X R N=NI t1(OH)zN=NRz -N=NRs which R, R1, R2 and'Rs are aryl radicals the two hydroxyl groups on R1 are ortho tothe azo.

groups, X represents groups such as halogen, alkyl, alkoxy, nitro,carboxyl, sulfonic, hydroxyl and hydrogen. '.At least one of'th'eradicals R w and R2 has a metallizable group ortho to the azo groupconnecting the-radical to R1 and at least ,one of the radicals R and R3has a solubilizing group.

In carrying out the present inventionfthe N polyazo dyes are metallizedwith one or more,

metals of the fourth group of the periodic table of elements. such aszirconium and titanium or combinations with other metals-such astitaniumchromium. These combinations of metals react with the dye toproduce'a product whichis not identical with th mixture of the productsobtained by treating portions of the dye withgseparate metals. Themetallic combination or'complex enters into the dye molecule in somemanner which is diiierent from the reaction of a single The precise formof chemi'calicombinaticular process of producing the dyes.

they will be prepared by coupling the dihydroxy metallizable groups.Such cases correspond to a species under the general formula in whichboth R and R2 contain hydroxyl 0r carboxyl groups ortho to the azogroups.

The presentinvention is not limited to a par- Normally compound with thediazo compoundand a diazo azo compound. Of course, the polyazo dyes maybe produced by successive couplings of diazo amino compounds which arethen rediazotized and further coupled, The endcomponents may be the sameor different.

Metallization is effected in the normal manner, for example, byrefiuxingan aqueous solution of the dye with salts or other suitable compounds ofthe metals or mixed metals. 1

In general, thenew dyes are dark colored powders which are quites0luble=in water and are capable ofv producingvaluable colors of variedtones. when dyed from an acid bath on wool,-si lk,- leather and furs.Thedyesshow good to excellent-fastness to light, washing, fulling, acid,alka- -lies and sea water: The degree of fastness will vary with theparticular dyes and with the metals used. The dyes of the class heredescribed, when metallized with zirconium or titanium exhibit ex.-cellentfastness to .light; Combinations of two 5 or more of these metalsalso give excellent results and combinations maybe made of one or moremetals belonging to other groups of the periodic system. l .1

The invention will be describedin detail in the followingexamples: butit should be understood that the invention is'not limited to the detailstherein set forth.

v Example 1 11.05 parts of picramateof sodaare suspended in parts ofwater and 'diazotized with 6.4 parts hydrochloric acid (real) and 3.66parts of sodium nitrite keeping thetemperature between 25 and 30 C. Theexcess of acidity is neutralized with asaturated solution of bicarbonateof soda. This diazo solution is thenv added to a solution containing5.88 parts of resorcinol in 200 parts of water and. 8.5xp'artsbicarbonate of soda. The mixture is stirred until coupling iscomplete'and 14.5 parts of soda ash added. Then a diazo solutionobtained 'by'treating 14.7 parts of amino azo benzene sulfonic acid in170 parts of water with 3.66 parts of "nitrite and 5.6 parts of acid at63 O. is added'and the mixture'stirre'd until couplingiscomplete. Thedye is salted out with sodium chlorideafter the solution is madeslightly acid to Congo red. The resulting dye paste is my OFFICE vdissolved in 800 parts of hot water and 12 parts of sodium acetateadded. The solution is heated to 60 C. and a solution containing partsof zirconium sulfate added. The entire mixture is then boiled for twohours and salted 'out with sodium chloride, filtered and dried at 65%70"C. The product is a dark brown powder, 'solublein water, producing a.brownish red color. It dyes animal fibers reddish tones of brown ofexcellent fastness. The formula for the dye priorto metallizationisasfollows: H

OaN

7 OzNa Example? 160 parts, of 1,5-dihydroxynaphthaleneis sus- 1 hours.

ling product is'a' dark powder producing neutral tones-of brown ofexcellent fastness.

pended in 2500 parts of water and. 400 parts. of

soda ash are added. The solution is cooled with ice to 510 C. and thenmixed with the diazo product obtained from 189 parts of2-aminophenol-4-sulfonic acid. The mixture is stirred until coupling iscomplete. obtained from 307 parts of the dye produced by couplingp-aminosalicylic acid with alpha naph-jthylamine in acid solution .isadded. .Suflicient sodium carbonate to'have thereaction alkaline V H{ff-Thej-formula for the dye prior to metallization is as follows;

on" 0H SOaNa V N=N HsC - OlNB I Example 4 11.05parts of picramate ofsoda are suspended in 50 parts of water and diazotized with 6.4 partshydrochloric acid ,(real) and 3.66 parts of sodium 7 nitrite keeping thetemperature between 25 and .Then the diazo compound throughout thecoupling is added. Thenthe mixtureis stirred until the secondcoupling'is .complete. The reaction must'be alkaline throughoutthe'couplin'g. The mixture .is then made acid to Congo andthe dye saltedoutwith. sodium chloride. Thev dye is filtered andthepaste suspended in6000 parts of water and treated with one mole of titanium nitrate, thenthe mixture isboiled for several hours. The resultingdye is then saltedout with sodium chloride. It is.soluble in water and dyes animal fibers:black. :Other metals mentioned in the specifications" may be substitutedfor tin .and similar metallized products obtained.

The formula for the is as follows:

dye prior to metallization .saltedoutiwith sodium chloride after thesolution ref brown tone.

is as follows:

30 C. The excess of acidity is neutralized with ,a saturated solution ofbicarbonate of soda. This diazo solution is then added to a solutioncontaining 5.88 parts of resorcinol in 200 parts of water and 8.5 partsof bicarbonate of soda. The mixture is stirred until coupling iscomplete and 14;.5 parts of soda ash added, Then a diazo solutionobtained by treating 14.7 parts of amino az'o benzene 'sulfonic acid'in'l70 parts of water with 3.66'parts of nitrite and 5.6 parts ofhydrochloric acid at 603-63 C. is added and the mixture stirred .untilcoupling is complete. The dye is is made ,slightly'acidtoCongo, red. Onemole equivalent of this dye is dissolved in 2000 parts of .water andmade slightly acid to Congo red. Two

'mole equivalent of sodium'acetate' is iadded and followed by 430 partsof zirconium. nitrate dis .s'olved'in water. The solution is boiled forthree hours and then treated with 10 parts of salt per parts by volumeand made slightly acid to Congo red."'. The dye is filtered and dried.It is a brown powder and dyes animal fibers a reddish The formula forthedye prior tometallization Example g g 154 parts ofp-nitro-o-amino-phenol are dissolved in 200 partsof water anddiazotizedwith the addition of 30 parts of 36% hydrochloric acid and 69parts of sodium nitrite at C. and cooled to 0-5 C.

160 parts of soda ash are added to the dye produced by coupling 277parts of amino azo benzene to 194 parts of hexyl resorcinol. I The nitroamino phenol diazo is added to this dye and coupling is allowed to stirover night. The dye is precipitated by addition of parts of sodiumchloride per 100 parts of volume and the dyeing is filtered.

One mole equivalent of this dyeis dissolved in 2000 parts of water andmade slightly acid to Congo red. Two mole equivalents of sodium acetateis added and followed by 430 parts of zirconium nitrate dissolved inwater. The solution is boiled for 3 hours and then treated with 10 partsof salt per 100 parts by volume and made slightly, acid to Congo red.The dyeis filtered and dried. It is a brown powder and dyes animalfibres a reddish brown tone.

The formula for the dye prior to metallization is as follows:

' C 01113 Example 6 The diazo equivalent to 27.7 parts of real amino azobenzene para sulfonic acid dissolved in 500 cc. of solution is coupledto 19.4 parts of hexyl resorcinol at 05 Cpill the presence of 50 partsof sodium acetate solution. 22.1 parts of sodium picramate are dissolvedin 400 cc. of water and heated until a solution is obtained. 30 parts of36% hydrochloric acid are added and the slurry is cooled to C. At 25-30C. it is diazotized with 6.9 parts of sodium nitrite dissolved in alittle water. After 45 minutes the diazotization is complete and theslurry is cooled to 0-5.-

16 parts of soda ash are added to the dye and the diazo picramic acid isadded and the coupling allowed to stir over night. The pH is thenadjusted to 6. A very faint trace of red shows on methyl red yellow andit is negative to brilliant yellow paper. The dye produced is filteredWithout the addition of salt.

One mole equivalent of this dye is dissolved in 2000 parts of water andmade slightly acid to Congo red. 1

Two mole equivalent of sodium acetate is added and followed by 430 partsof zirconium nitrate dissolved in water. The solution is boiled forthree hours and then treated with 10 parts of salt per 100 parts'byvolume and made slightly acid to Congo red. Thedye is filtered anddried. It is a brown powder and dyes animal fibers a reddish brown tone.

The dye prior to metallization has the following formula:

0 6H13 Example 7 in 400 parts of water and stirred to complete soareadded and hydrochloric acidis added until there is a faint but permanenttest on Congo red paper. It is filtered after it had been stirredfor'several hours to allow complete precipitation.

One mole equivalent of this dye is dissolved in 2000 parts of water andmade slightly acid to Congo red. Two mole equivalents of sodium acetateare added and followed by 430 parts of zirconium nitrate dissolved inwater. The solution is boiled for three hours and then treatedwith 10parts of salt per 100 parts by volume and made slightly acid to Congored. The dye is filtered and dried. It is a brown powder and dyes animalfibres a brown tone. The formula for the dye prior to'neutralization isas follows:

OH on OH HOaSN=NN=N NN No,

' S0311 S0511 j N02 Example 8 One mole equivalent of the dye having thefollowing formula:

SOeN'a is dissolved in 2000 parts of Water and made slightly acidtoCongo red. Two mole equivalents of sodium acetate are added and followedby one-half mole equivalent of each titanium sulfate and chromiumsulfate. The solution is boiled for four hours and then treated with 10parts of salt per 100 partsof solution by volume and made slightly acidto Congo red. The'dye is filtered and dried. It is a brown powder anddyes animal fibres a reddish brown tone.

Example 9 The dye of Example 8 metallized with zirconium and copperproduces a complex brown dye and dyes animal fibres a reddish tone.

The unmetallized dye compounds described in the present applicationwherein the middle component is hexylresorcinol are new chemicalcompounds and are not claimed as a part of the present invention Whichis limited to the fourth group of the periodic table of elements.

What We claim is:

1. Metallized azo dyes having the following formula:

hydroxyl groups on R1 are ortho, to the azo in which R1 is a radical ofthe benzene series and R, R2 and R3 are aryl radicals, the hydroxylgroups on R1 being ortho to the two a zo groups and X represents amember of the group consisting of halogen, alkyl, alkoxy, nitro,carboxyl, sulfonic, hydroxyl, and hydrogen, at least one of the radicalsR and R2 have a metallizable group ortho to the azo group connecting theradical with the resorcinol radical and at least one of the radicals Rand Ra-has a solubilizing group, and the dye being metallized with atleast one of the metals included in the group consisting of fourth groupof elements in the periodic table.

3. Metallized azo dyes, the azo dye component of which has the followingformula:

in which the radicals R, R2 and R3 are aryl radicals, R1 is a radical ofthe naphthalene series having the hydroxyl groups ortho to the azogroups and X represents a member of the group consisting of 'halogen,alkyl, alkoxy, nitro, carboxyl, sulfonic, hydroxyl, and hydrogen, atleast one of the radicals R and R2 having a metallizv able group orthoto the azo group connecting the radical R1, and at least one of theradicals R and R3 containing a solubilizing group, and the dye beingmetallized with at least one of the metals included in the groupconsisting of fourth group of elements in the periodic table.

4. A metallized azo dye according to claim 1 in which both R and R2contain metallizable groups ortho to the azo groups connecting theseradicals with R1.

5. A metallized azo dye according to claim 1 in whichRz is anarylazoaryl radical.

' 6.'A metallized azo dye according to claim 1 in which R3 is an arylradical free from azo groups except the one connecting to R2.

7. A metallized azo dye according to claim 2 in which R is phenol withthe hydroxy group ortho to the azo group and R2 is an azobenzeneradical.

8. A metallized azo dye according to claim 2 in which R is N0; 9. Ametallized trisazo dye of the general formula:

HO OH NO: in which R2 represents a radical of a 4-sulfonic acidazobenzene, the dye being metallized with at least one metal included inthe group consisting of elements of the fourth group of the periodictable.

10. A metallized azo dye according to claim 1 in which both R and R2contain metallizable groups ortho to the azo groups connecting theseradicals to R1 and the dye metallized with a mixture of at least one ofthe metals included in the group consisting of elements in thefourthgroup of the periodic table, with at least one of the metalsincluded in the group consisting of fourth group of elements in theperiodic table.

11. A complex zirconium copper compound of the azo dye having thefollowing formula:

H OH

I OaNa 12. A metallized azo dye according to claim 1 in which X ishexylresorcmol.

13. A metallized azo dye according to claim 1 in which x iz oH 1 ischromotropic acid.

, MOSES L. CROSSLEY. LINCOLN M. SHAFER.

CERTIFICATE OF CORRECTION. Patent No. 2,259,756. October 21, 19141.

MOSES L. CROSSIEY, ET AL.

It is hereby certified that error-appears in the printed specificationof the above numbered patent requiring correction as follows: Page-Lsec-- 0nd column, line 1+1, claim 11 in the extreme left-hand portion ofthe formula, for "Q 8" read --NaO S-; and that the said Letters Patentshould be read with this correction therein that the same may conform tothe rec- 0rd. of the case in the Patent Office.

Signed and sealed this 18th day of November, A. D. 19141.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

